Photoresist formulation for high aspect ratio plating

ABSTRACT

SU-8 photoresist compositions are modified to improve their adhesion properties by adding 1% to 6% of an adhesion promoter selected from the group consisting of glycidoxypropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and aminopropyltrimethoxysilane. SU-8 photoresist compositions are modified to improve their resistance to cracking and film stress by adding 0.5% to 3% of a plasticizer selected from the group consisting of dialkylphthalates, dialkylmalonates, dialkylsebacates, dialkyladipates, and diglycidyl hexahydrophthalates. The improvements can be obtained simultaneously by adding both the adhesion promoter and the plasticizer to SU-8 photoresist compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.10/853,858, filed May 26, 2004, now U.S. Pat. No. 7,005,233, andpublished as U.S. Patent Application Publication No. 2004/0214098, whichis a continuation of U.S. patent application Ser. No. 10/027,437, filedDec. 21, 2001 and published as U.S. Patent Application Publication No.2003/0138731 (abandoned).

FIELD OF THE INVENTION

The present invention relates generally to photoresist masks for highaspect ratio plating on semiconductor circuit boards, and moreparticularly to improvements in negative photoresist masks made fromoctafunctional epoxidized novolac resins such as SU-8.

BACKGROUND OF THE INVENTION

Negative photoresist masks are commonly employed in lithographicprocesses used to build integrated circuit boards. As is known in theart, lithography is a process by which geometric shapes are transferredfrom a mask onto the surface of a substrate. These geometric shapes,when transferred onto the surface of a silicon wafer, make up the partsof the circuit, such as gate electrodes, contact windows, probeelectrodes, switches, metal interconnections, and the like.

The steps of the lithographic process are generally as follows. First, abase semiconductor (e.g., silicon) substrate is provided, and a secondmaterial layer, such as an oxide layer, is formed thereon. Next, aphotosensitive polymer film or photoresist layer is deposited on thewafer, evenly covering the second material layer. Then, the photoresistlayer is selectively fixed to produce a desired pattern thereon. This isdone by selectively exposing the photoresist layer with ultravioletlight or other radiation, with the selective exposure defining thedesired pattern.

Then, the unfixed portions of the photoresist layer are removed by asolvent rinse. (The unfixed portions may be either the exposed ornon-exposed areas of the photoresist layer depending upon the type ofpolymer used.) At this point the surface of the wafer is covered by asubstrate and a second material layer, with a desired design “masked”thereon.

The next step is to etch away the exposed second material layer whileleaving the fixed portions of the photoresist layer intact. This istypically done by etching with an etchant that attacks the secondmaterial layer but not the photoresist layer, such as by hydrofluoricacid (HF), etching the exposed silicon dioxide (SiO₂) while leaving theHF-resistant polymer photoresist layer intact. Excess etchant is rinsedaway after the etching step, followed by a chemical removal of thephotoresist layer with a solvent solution. The wafer is then rinsed toremove excess solvent and is now ready for the next photoresist step tooccur.

A typical IC device requires between about five and 30 lithographicdeposition layers, more if the device is fairly complex. Each of thoselayers corresponds to a separate type of device in the circuit, such asgate electrodes, contact windows, probe electrodes, switches, metalinterconnections, and the like.

It can be seen from the above that the photoresist masking material mustadhere firmly to the substrate, and must maintain planarity to very hightolerance levels.

One group of commonly used photoresist materials are those based onoctafunctional epoxidized novolac resins, and particularly those basedon the SU-8 family of photoresists made from Shell Chemical's EPON® SU-8epoxy resin. The SU-8 photoresist materials are negative, epoxy-type,near-UV photoresist materials. The SU-8 family of photoresist materialsis popular because it can provide relatively thick-film (2 mm or larger)photoresist films having aspect ratios greater than 20 at relatively lowcosts. In addition to being a relatively thick-film photoresistmaterial, SU-8 is well suited for acting as a mold for electroplatingbecause of its relatively high thermal stability (T_(g) greater than 200degrees C. for the cross-linked or post-exposure photoresist material).

While the SU-8 family of photoresist materials enjoys relatively wideuse and positive results as a photoresist in IC lithography, its utilityis somewhat limited for use with silicon wafers greater than three orfour inches in diameter. As with most polymer photoresists, the SU-8family of photoresist materials is prone to delamination and viacracking arising from high film stress when used with relatively largesilicon wafers.

Another problem with the SU-8 family of photoresists arises fromadhesion problems with certain substrate materials. For example, SU-8does not adhere as readily to metallic copper as it does to copperoxide.

The IC device industry is constantly demanding larger and/or morecomplex devices. As the size and complexity of the demanded IC devicesincrease, the need arises for a photoresist material having reduced filmstress and increased adhesion properties for use in the lithographyprocess to make such devices. The present invention addresses that need.

SUMMARY OF THE INVENTION

Briefly describing one aspect of the present invention, there isprovided a photoresist composition for high aspect ratio lithography.The composition comprises an octafunctional epoxidized novolac resinsuch as SU-8, an organic solvent, a photopolymerization initiator, aplasticizer, and an adhesion promoter. The adhesion promoter iseffective for improving the adhesion of the mask, particularly ontocopper-based substrates. The plasticizer reduces delamination and viacracking between the photoresist film and the substrate, making largerwafers commercially viable.

One object of the present invention is to provide an improvedphotoresist composition for lithographic processes.

Further aspects and advantages of the present invention will be apparentfrom the following description.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For the purposes of promoting an understanding of the principles of theinvention, reference will now be made to the preferred embodiments andspecific language will be used to describe the same. It willnevertheless be understood that no limitation of the scope of theinvention is thereby intended, with such alterations and furthermodifications of the described embodiments being contemplated as wouldnormally occur to one skilled in the art to which the invention relates.

As indicated above, one aspect of the present invention is an improvednegative photoresist composition. In one preferred embodiment thecomposition comprises an octafunctional epoxidized novolac resin, anorganic solvent, a photopolymerization initiator, a plasticizer, and anadhesion promoter. The inventive photoresist masking composition hasimproved adhesion on copper-based substrates, and resists cracking andother film stresses so that larger MEMS wafers can be made.

Referring first to the components of the preferred composition, thephotoresist composition of the present invention comprises anoctafunctional epoxidized novolac resin appropriate for buildinghigh-aspect ratio masks for MEMS lithography. The preferred resin isEPON® SU-8 epoxy resin, available from the Shell Chemical Company. Thatresin is described by the formula:

In the inventive masking compositions the resin is preferably present inan amount ranging from about 50% to about 75%. More preferably, theresin comprises between about 60% and 65% of the masking composition,with 62% to 63% resin being most preferred.

As is known to the art, a solvent is typically used to make epoxy-resinbased masking compositions. In the preferred embodiment the solvent isan organic solvent with a boiling point of between about 160° C. and260° C. More preferably the solvent has a boiling point of between about190° C. and 220° C. The most preferred solvent is γ-butyrolactone, witha boiling point of about 205° C.

The solvent is preferably present in an amount ranging from about 15% toabout 45%. In the more preferred embodiments about 20–30% solvent isused, with about 25% solvent being used in the most preferredembodiment.

The photoresist composition also includes a photopolymerizationinitiator. As is known to the art, the photopolymerization initiator isa material that promotes cross-linking of the resin when exposed tooptical radiation. The cross-linking makes the resin insoluble to thedeveloping solution used to pattern the semiconductor device.

One class of photopolymerization initiator (hereinafter alternativelyreferred to as either a photoinitiator or a cationic initiator) usefulfor the present invention is the class of triaryl sulphonium SbF₆ salts.For example, Cyracure® 6974, available from the Union Carbide Corp., isparticularly preferred.

The photoinitiator is preferably present in an amount ranging from about3% to about 10%. More preferably the initiator is present in an amountranging from about 5% to about 8%, with about 6% to about 7%photoinitiator being most preferred.

An adhesion promoter is preferably added to the masking compositions toimprove its adhesion characteristics (i.e., increase the relativetackiness of the composition and/or increase the scope of materials towhich the composition significantly adheres). The adhesion promoter ispreferably a member selected from the group consisting ofglycidoxypropanetrimethoxysilane, mercaptopropyltrimethoxysilane, andaminopropyltrimethoxysilane.

In the most preferred embodiment the adhesion promoter isglycidoxypropanetrimethoxysilane (GPTMS). In other preferred embodimentsthe adhesion promoter is another silicone containing adhesion promoter,such as mercaptopropyltrimethoxysilane (MPTMS) oraminopropyltrimethoxysilane (APTMS). Any of these adhesion promoters, orothers, may be use alone or in combination as desired to tailor theadhesion characteristics of the mask. For example, MPTMS is particularlyuseful as an adhesion promoter when the composition is desired to adhereto gold.

The adhesion promoter is preferably added in concentrations of betweenabout 1 and about 6 weight percent. Concentrations of between about 3%and about 4% are more preferred in testing to date. Since the adhesionpromoter can affect the viscosity of the composition (hamperingdeposition of the composition as a film) and/or promote phase separationof the composition (resulting in an inhomogeneous film withinhomogeneous physical, chemical, and/or mechanical properties), thosefactors should be taken into account when selecting adhesion promoterconcentration levels.

A plasticizer is preferably added to the masking composition to reducefilm stresses and allow the manufacture of larger (e.g., 8″) wafers. Theplasticizer is preferably a member selected from the group consisting ofdialkylphthalates, dialkylmalonates, dialkylsebacates, dialkyladipates,and diglycidyl hexahydrophthalates.

In the most preferred embodiment the plasticizer is dioctylphthalate(DOP). Other preferred plasticizers include the dialkyl esters ofdicarboxylic acids, wherein the dicarboxylic acids are between 1 and 18carbon atoms in length (such as, for example, dialkylphthalates,dialkylsebacates, dialkylmalonates, dialkyladipates and the like).Epoxy-containing plasticizers such as diglycidyl hexahydrophthalate maybe also used.

It should be noted that the phthalates have positional isomers, butthese do not substantially affect their effectiveness as plasticizers.Likewise, the alkyl groups may be straight chain, branched chain,aromatic and/or cyclic. These plasticizers may be added, either alone orin combination, to tailor the plasticity of the resultant composition.

The plasticizer is preferably added in an amount sufficient tosubstantially reduce film stresses in films spun from about 5 to 500 μmthick, but is insufficient to cause excessive softening of thecomposition to the extent that contact printing difficulties arise.Also, excessive plasticizer can decrease the photo speed of the film.Therefore, plasticizer is added in an amount sufficient to substantiallyreduce film stress but insufficient to adversely affect film photo speedor contact printability. In the preferred embodiments the plasticizer ispresent in amounts ranging from 0.5 weight percent to 3.0 weightpercent.

As to how to make and use the inventive compositions, the epoxy-basedphotoresist compositions are preferably prepared by dissolving the epoxyresin in the organic solvent to form a solution. The plasticizer is nextadded to the solution and the solution is mixed to substantially achieveuniformity. Next, the cationic initiator is separately added to thesolution and the solution is again mixed until substantially uniform.Finally, the adhesion promoter is added to the solution and the solutionis immediately mixed to result in a substantially uniform or homogeneoussolution.

While the additives (i.e., the plasticizer, the adhesion promoter andthe cationic initiator) may be added in any convenient order, the abovesequence is preferred likewise, while mixing the solution after theaddition of each of additives is preferred, mixing may be delayed untiltwo or all of the additives have been added to the solution. Thoroughand immediate mixing is preferred after the addition of the adhesionpromoter to minimize reaction of the adhesion promoter with theremaining ingredients of the solution; delayed or incomplete mixing canresult in gel formation.

After mixing, the solution may be milky due to air entrapment during themixing process, and natural debubbling is preferred by storing themixture in an amber glass container or the like and/or in a darkenvironment for a sufficient time for the entrapped gas to escape fromthe solution.

As discussed above, devices may be built on semiconducting wafers by aseries of photolithographic processing steps. In the firstphotolithographic step, the photoresist film may be applied to a siliconwafer by methods known in the art, such as by spin deposition. Thethickness of the film is a function of the coating process (such as theRPM chosen during spin deposition, spin deposition time, and the like),the viscosity of the photoresist composition, the amount of photoresistcomposition used, and the like. Typically the film is between about 1micron and about 200 microns thick, with film thicknesses of betweenabout 50 microns and 200 microns commonly being prepared.

After the wafer has been coated with the photoresist film, the wafer isdried to remove excess solvent. Drying may be accelerated by apre-exposure bake of the wafer. Typically the pre-exposure bake lastsbetween 3 and 5 hours at a temperature approaching about 80–95 degreesC. The photoresist film is fixed by selectively exposing it to highenergy electromagnetic radiation, preferably ultraviolet ornear-ultraviolet light, on the order of from about 500 to 2500 mJ. Afterfixing, the film undergoes a post-exposure bake (PEB) at about 55° C.for a predetermined length of time, typically up to 1 or 2 hours.

Unfixed photoresist film is removed with a solvent and furtherprocessing of the wafer such as deposition of material and/or etching ofmaterial is done at this time. After these device processing andbuilding steps have been completed, the photolithographic process isthen repeated to build the next step in the series.

Reference will now be made to specific examples using the compositionsand methods described above. It is to be understood that the examplesare provided to more completely describe preferred embodiments, and thatno limitation to the scope of the invention is intended thereby.

EXAMPLE 1 Preparation of Unmodified SU-8 Masking Composition.

A two-step process is used to produce SU-8 photoresist without adhesionand plasticity modification.

Stock Solution. In a 2 L mixing container equipped with a mechanicalstirrer or roller add 624 g of solid Epon SU-8 resin and 262 g ofGama-butyrolactone. The mixture is allowed to soak with occasionalagitation until a viscous homogeneous solution is formed. This is a slowdissolution process and may take between 1–5 days to complete. Theprocess can be accelerated by heating to about 60° C. if needed. Makesure the container is properly sealed during the process so that waterabsorption is kept to a minimum.

The solution then can be filtered through a 5 μm filter at room orelevated temperature to ensure gel-free resin stock solution. The aboveoperation can be performed under normal lighting.

Final mixture. To 886 g of the resin stock solution under yellow light,add 63 g of filtered Cyracure® 6974 and mix with a mechanical stirreruntil a uniform solution is formed (800 rpm for 20 min).

EXAMPLE 2 Preparation of Modified SU-8 Masking Composition.

A two-step mixing process is also used to produce the modified GD41solution:

Stock Solution. In a 2 L mixing container equipped with a mechanicalstirrer or roller add 624 g of solid Epon SU-8 resin, 262 g ofGama-butyrolactone, and a 10 g of dioctyl phthalate (DOP). The mixtureis allowed to soak with occasional agitation until a viscous homogeneoussolution is formed. This is a slow dissolution process and may takebetween 1–5 days to complete. The process can be accelerated by heatingto about 60° C. if needed. Make sure the container is properly sealedduring the process so that water absorption is kept to a minimum. Thesolution is then filtered through a 5 μm filter at room or elevatedtemperature to ensure gel-free resin stock solution. The above operationcan be performed under normal lighting.

Final mixture. To 896 g of resin stock solution under yellow light, add64 g of filtered Cyracure® 6974 and mix with a mechanical stirrer untila uniform solution is formed (about 800 rpm for 10 min). Forty grams offiltered glycidoxypropranetrimethoxysilane (GPTMS) is then added andmixed at about 800 rpm for 20 min. The final blend should be uniformlymilky due to air entrapment during mixing and natural debubbling bystoring the mixture in an amber glass container in a dark cabinet shouldbe completed within 36 hours. Both Cyracure® 6974 andglycidoxypropranetrimethoxysilane should be filtered by 1 μm syringefilters prior to addition to the resin stock solution. Since GPTMS inits concentrated form will react with the remaining ingredients to forma gel, it is desirable to minimize the delay between addition and mixingto avoid gel formation.

EXAMPLE 3 Preparation of Alternative Modified SU-8 Masking Composition.

A photoresist composition was made by combining the following componentswith mixing: 62.4% SU-8 resin, 26.3% γ-butyrolactone, 6.3% Cyracure®6974, 1% DOP, and 4% GPTMS, all on a weight percent basis. Thephotoresist was prepared under yellow light, stored in an opaquecontainer, and allowed to debubble. The coating was applied to copperseed silicon wafers, was dried, exposed, and submitted to a PEB toprovide a photoresist film with superior adhesion and film stressproperties.

EXAMPLE 4 Preparation of Alternative Modified SU-8 Masking Composition.

A photoresist composition was made by combining the following componentswith mixing: 60% SU-8 resin, 27% γ-butyrolactone, 6% Cyracure® 6974, 1%percent DOP, and 6% GPTMS, all on a weight percent basis. Thephotoresist was prepared under yellow light, stored in an opaquecontainer, and allowed to debubble. The coating was applied to copperseed silicon wafers, was dried, exposed, and submitted to a PEB toprovide a photoresist film with superior adhesion and film stressproperties.

EXAMPLE 5 Preparation of Modified SU-8 Masking Composition withoutAdhesion Improver.

A photoresist composition was made by combining the following componentswith mixing: 60% SU-8 resin, 30% γ-butyrolactone, 7% Cyracure® 6974, and3% percent DOP, all on a weight percent basis. The photoresist wasprepared under yellow light, stored in an opaque container, and allowedto debubble. The coating was applied to copper seed silicon wafers, wasdried, exposed, and submitted to a PEB to provide a photoresist filmwith superior film stress properties.

EXAMPLE 6 Preparation of Modified SU-8 Masking Composition withoutPlasticizer.

A photoresist composition was made by combining the following componentswith mixing: 65% SU-8 resin, 23% γ-butyrolactone, 6% Cyracure® 6974, and6% GPTMS, all on a weight percent basis. The photoresist was preparedunder yellow light, stored in an opaque container, and allowed todebubble. The coating was applied to copper seed silicon wafers, wasdried, exposed, and submitted to a PEB to provide a photoresist filmwith superior adhesion properties.

EXAMPLE 7 Verification of Improved Adhesion Properties.

Physical tests to measure the difference in adhesion between modifiedand unmodified SU-8 epoxy resin-based photoresist materials wereconducted. The two resins (modified and unmodified) were preparedgenerally as described above. The modified masking composition comprisedabout 62.4 weight percent SU-8 resin, 26.3 weight percentγ-butyrolactone, 6.3 percent Cyracure® 6974, 1.0 percent DOP, and 4.0percent GPTMS. Each composition was applied to an untreated copper seedwafer.

Adhesion was measured by a block shearing method, wherein each block isa 210 micron square with a thickness of approximately 140 microns. Bothsystematic die site and random walk sampling were taken. The die site isdefined by the central 12 by 16 die array with (1, 1) being the lowerleft corner die. Using die site sampling, the wafer average sheer forcefor the unmodified SU-8 material was 49.5 grams while the wafer averagesheer force for the modified SU-8 material was 63.6 grams, showing a 28percent improvement over the unmodified SU-8. Likewise, for the randomwalk testing, the wafer average sheer for the unmodified SU-8 was 51.3grams while the wafer average for the modified SU-8 was 61.2 grams,showing an improvement of 19 percent.

The Tables below show the results.

TABLE I Adhesion test of unmodified SU-8 by block shearing on untreatedCu seed wafers. Each block is a 210 um square with thickness ~140 um.Both systematic die site and random walk sampling were taken. Die siteis defined by the central 12 × 16 die array with (1, 1) being thelower-left corner die. SU-8 on Cu, No ash, Test speed: 50 um/s Landspeed: 250 um/s Shear height: 10 um Overtravel 10 um Shear (g) Shear (g)Shear (g) Die n = 20 Die n = 20 Die n = 20 1, 1 42.02 (4.44) 1, 6 44.75(2.80) 1, 12 37.46 (8.79) 8, 1 41.09 (1.81) 8, 6 48.14 (3.10) 8, 1242.25 (4.03) 16, 1  64.91 (5.40) 16, 6  61.49 (3.84) 16, 12  63.39(2.99) Wafer average, 9 die, 49.5 (4.13) g shear force, n = 180 Waferaverage, random walk, 51.32 (7.94) g shear force, n = 100

TABLE II Adhesion test of modified SU-8 according to the presentinvention by block shearing on untreated Cu seed wafers. Each block is a210 um square with thickness ~140 um. Both systematic die site andrandom walk sampling were taken. Die site is defined by the central 12 ×16 die array with (1, 1) being the lower left-corner die. Modified SU-8on Cu, No ash, Test speed: 5-um/s Land speed: 250 um/s Shear height: 10um Overtravel: 10 um Shear (g) Shear (g) Shear (g) Die n = 20 Die n = 20Die n = 20 1, 1 59.02 (2.15) 1, 6 59.02 (2.15) 1, 12 57.70 (5.05) 8, 164.64 (3.61) 8, 6 64.64 (3.61) 8, 12 63.72 (1.58) 16, 1  66.99 (4.85  16, 6  66.99 (4.85) 16, 12  67.45 (6.82) Wafer average, 9 die, 63.55(3.54) g shear force, n = 180 Waver average, random walk, 61.21 (8.59) gshear force, n = 100

EXAMPLE 8 Verification of Improved Resistance to Cracking and FilmStress.

Physical tests to measure the difference in resistance to cracking andfilm stress for modified and unmodified SU-8 epoxy resin-basedphotoresist materials were conducted. The two resins (modified andunmodified) were prepared generally as described above. The modifiedmasking composition comprised about 62.4 weight percent SU-8 resin, 26.3weight percent γ-butyrolactone, 6.3 percent Cyracure® 6974, 1.0 percentDOP, and 4.0 percent GPTMS.

In the first test, the via cracking frequency for wafers coated withmodified and unmodified SU-8 was measured. As is known to the art, viacracking arises from differences in the thermal expansion between thefilm and the substrate and is measured as a function of ultravioletexposure dosage and cooling rate after the PEB. The cooling rate isgiven as either “fast” or “slow”, with “fast” being defined as coolingfrom 90° C. to about 22° C. in about 4 minutes and “slow” being definedas cooling from 90° C. to about 22° C. in about 20 minutes.

As is apparent from Table III, the modified SU-8 photoresist materialtrends towards having a substantially lower percentage of via crackingthan does the unmodified SU-8 photoresist film material under the sameconditions.

TABLE III Via cracking frequency and photodose/PEB cooling correlationfor photoresist coatings on a wafer substrate. Only circular vias in thearray were counted. Q1, Q2, etc. represent quadrants with Q1 beingupper-left corner with flat facing down, clockwise to Q4. 40 vias ineach quadrant were counted. Fast cooling is defined as a rate of ~4 min.from 90° C. to 22° C.; slow cooling is defined as a rate ~20 min. from90° C. to 22° C.; NA indicates catastrophic failure of the wafersubstrate. Die position Die position Photo PEB with % via cracking with% cracking dose cool- (Modified SU-8) (SU-8) MJ/cm2 ing Q1 Q2 Q3 Q4 Q1Q2 Q3 Q4 1200 Fast 100 100 100 100 100 100 100 100 1200 Fast 70 80 10065 100 100 100 100 1200 Slow 20 40 15 25 NA NA NA NA 1200 Slow 33 30 4033 NA NA NA NA 1570 Fast 40 33 40 33 100 90 100 80 1570 Fast 75 100 9085 100 100 100 100 1570 Slow 40 60 50 53 NA NA NA NA 1570 Slow 55 30 5540 NA NA NA NA 1940 Fast 100 80 90 60 80 100 100 95 1940 Fast 90 85 7580 100 90 100 85 1940 Slow 42 58 33 53 NA NA NA NA 1940 Slow 60 35 55 40NA NA NA NA 2310 Fast 60 45 30 40 100 100 90 100 2310 Fast 65 53 75 4580 90 85 100 2310 Slow 5 10 15 0 30 20 60 28 2310 Slow 5 25 0 15 20 4023 50

In a second test, real time wafer bow was measured for wafers coatedwith modified and unmodified SU-8 masks. All wafers were baked at 90° C.for 3 hours, and both after solvent bake bow and after PEB bow weremeasured after a 30 minute room temperature cooling period.

As can be seen from the data, the modified SU-8 films had substantiallyless wafer bow than did their unmodified counterparts when tested underthe same conditions.

TABLE IV Real-time wafer bow monitoring for 90 C./3 hour bake. Bothafter solvent bake and after PEB bow were measured after 30 minute roomtemperature cooling. Formulation Modified SU-8 SU-8 Mask Film Dot DotFilm Dot Dot Bask Temp C./Time (hrs) 90/3 90/3 90/3 90/3 90/3 90/3Before coat 32 40 NA 25 33 NA After solvent bake 66 74 74 97 101 108After expose 44 42 63 55 55 83 After PEB 310 95 98 330 125 132 AfterDevelop 300 39 50 300 45 48

While the invention has been illustrated and described in detail in thedrawings and foregoing description, the same is to be considered asillustrative and not restrictive in character, it being understood thatonly the preferred embodiment has been shown and described and that allchanges and modifications that come within the spirit of the inventionare desired to be protected.

1. A method comprising: providing a photoresist material, the photoresist material comprising: an octafunctional epoxidized novolac resin;an organic solvent; a photopolymerization initiator; a plasticizerselected from the group consisting of dialkylphthalates,dialkylmalonates, dialkylsebacates, and dialkyladipates; and an adhesionpromoter selected from the group consisting ofglycidoxypropanetrimethoxysilane, mercaptopropyltrimethoxysilane, andaminopropyltrimethoxysilane; depositing the photoresist material on asubstrate; selectively exposing the deposited photoresist material toradiated energy, one or more portions of the photoresist being hardenedand one or more portions of the photoresist being unhardened; andremoving the one or more unhardened portions of the photoresist materialfrom the substrate.
 2. The method of claim 1, wherein the plasticizer isa dialkylphthalates.
 3. The method of claim 1, wherein the plasticizeris a dialkylmalonates.
 4. The method of claim 1, wherein the plasticizeris a dialkylsebacates.
 5. The method of claim 1, wherein the plasticizeris a dialkyladipates.
 6. The method of claim 1, wherein the adhesionpromoter is a glycidoxypropanetrimethoxysilane.
 7. The method of claim1, wherein the adhesion promoter is a mercaptopropyltrimethoxysilane. 8.The method of claim 1, wherein the adhesion promoter is aaminopropyltrimethoxysilane.
 9. The method of claim 1, wherein theoctafunctional epoxidized novolac resin is of the formula:


10. The method of claim 1, wherein the solvent is present in an amountranging between about 15% and about 45% by weight.
 11. The method ofclaim 1, wherein the solvent is present in an amount ranging betweenabout 20% and about 30% by weight.
 12. The method of claim 1, whereinthe solvent is present in an amount of about 25% by weight.
 13. Themethod of claim 1, wherein the photopolymerization initiator is presentin an amount ranging between about 3% and about 10% by weight.
 14. Themethod of claim 1, wherein the photopolymerization initiator is presentin an amount ranging between about 5% and about 8% by weight.
 15. Themethod of claim 1, wherein the photopolymerization initiator is presentin an amount ranging between about 6% and about 7% by weight.
 16. Themethod of claim 1, wherein the photopolymerization initiator is atriaryl sulphonium SbF₆ salt.
 17. The method of claim 1, wherein theplasticizer is present in an amount ranging between about 0.5% and about3% by weight.
 18. The method of claim 1, wherein the plasticizer ispresent in an amount of about 2% by weight.
 19. The method of claim 1,wherein the adhesion promoter is present in an amount ranging betweenabout 1% and about 6% by weight.
 20. The method of claim 1, wherein theadhesion promoter is present in an amount ranging between about 3% andabout 4% by weight.
 21. The method of claim 1, wherein: the substratecomprises copper or a wafer; and the radiated energy comprises opticalradiation, electromagnetic radiation, ultraviolet radiation, or nearultraviolet radiation.
 22. A method comprising: providing a photoresistmaterial, the photo resist material comprising: an octafunctionalepoxidized novolac resin; an organic solvent having a boiling pointbetween 160° C. and 260° C.; a photopolymerization initiator; aplasticizer selected from the group consisting of dialkylphthalates,dialkylmalonates, dialkylsebacates, dialkyladipates, and diglycidylhexahydrophthalates; and an adhesion promoter selected from the groupconsisting of glycidoxypropanetrimethoxysilane,mercaptopropyltrimethoxysilane, and aminopropyltrimethoxysilane;depositing the photoresist material on a substrate; selectively exposingthe deposited photoresist material to radiated energy, one or moreportions of the photoresist being hardened and one or more portions ofthe photoresist being unhardened; and removing the one or moreunhardened portions of the photoresist material from the substrate. 23.The method of claim 22, wherein the solvent has a boiling point ofbetween 190° C. and 220° C.
 24. The method of claim 22, wherein thesolvent has a boiling point of between 200° C. and 210° C.
 25. Themethod of claim 22, wherein: the substrate comprises copper or a wafer;and the radiated energy comprises optical radiation, electromagneticradiation, ultraviolet radiation, or near ultraviolet radiation.
 26. Amethod comprising: providing a photoresist material, the photo resistmaterial comprising: an octafunctional epoxidized novolac resin; anorganic solvent comprising gamma butyrolactone; a photopolymerizationinitiator; a plasticizer selected from the group consisting ofdialkylphthalates, dialkylmalonates, dialkylsebacates, dialkyladipates,and diglycidyl hexahydrophthalates; and an adhesion promoter selectedfrom the group consisting of glycidoxypropanetrimethoxysilane,mercaptopropyltrimethoxysilane, and aminopropyltrimethoxysilane;depositing the photoresist material on a substrate; selectively exposingthe deposited photoresist material to radiated energy, one or moreportions of the photoresist being hardened and one or more portions ofthe photoresist being unhardened; and removing the one or moreunhardened portions of the photoresist material from the substrate. 27.The method of claim 26, wherein: the substrate comprises copper or awafer; and the radiated energy comprises optical radiation,electromagnetic radiation, ultraviolet radiation, or near ultravioletradiation.